Azo compounds and material colored therewith



nucleus, R1 represents oration of organic derivatives of and wool. Coloration can be effected by dyeing,

. 2,373,700 AZO COMPOUNDS ANDM'ATERJA COLORED THEREWITH: mes G. McNallyand Josephli i bickefll't' Jersey No Drawing.

ester, N. 72., assignors to pain; R che t N; Y-,

Eastman Kodak Coma corporation of New ppllcatlon June 29. 1940,

Serial No. 343,2li 4.

claims; 31. zoo-2st This invention relates to new azo dye compounds and their application to the art of coloring.

We have discovered that the azo compounds having the general formula:

wherein R represents I the residue of 1a member selected from the group consisting of a'benzene, a naphthalene, a benzoxazole and a benzothiazcle the residue of a member selected from the group consisting of a benzene and a naphthalene nucleus containing but one benzene and naphthalene ring, respectively, R2

. represents a member selected from the group consisting of hydrogen, an aliphatic group, a cycloalkyl group, a furyl group, a phenyl nucleus and a group is attachedto the nucleus represented by R1 in para position to the azo bond shown con- 'stitute 'a" valuable class of dye compounds. Depfending upon their structure, the azo compounds 'of our invention possess application for thecolcellulose," silk printing, stenciling or like methods.

Whi1e our invention relates broadly to azo com- "pounds'having the formula above given; it relates andfsilk; Another object of our invention is to more particularly to those compoundsjwherein R and vR1 are benzene nuclei, R2 is hydrogen or alkyl andY isjalkyl'. Ordinarily, X is a saturated aliphatic hydrocarbon chain containing 1 -4 inclusivecarbon atoms and normally it o f Both sulf nated and non-sulfonated compounds areincludedwithin the scope. of our invention. '1 The nuclear non-sulfonated compounds have been found to be especially of value for the dyeing ofbrgan'ic derivatives oicellulose and it is to these compounds and, their application for the dyeingof'organic derivatives of cellulose that ourinventionis Particularly directed. The nuclear? non-sul fonated compounds likewise possess someapplication, for the dyeing of wool and silk. For the dyeing of organic derivativesof cellulose, such as cellulose acetate'silk, nuclear non-sulionated: dye compounds wherein R. and R1 are benzene nuclei are generally advantageous.

The'i'nuclear sulfonated compounds of our inventionhavelittle or no utility for the dyeing of organic derivatives of cellulose but possess applicationiforjthe dyeing of wool and silk. Preferablywhen the dye compounds of our invention are to! be employed forthe dyeing of organic derivatives of cellulose they should contain no nuclear freecarboxylic acidxgroup. Red, yellow, orange-yellow, orange-red, greenish-blue, blue and violet dyeings, for example, can be obtained employing the dye compounds of our invention.

It is an object of our invention to provide a new class of azo dye compounds suitable for the coloration oforganic derivatives of cellulose, wool *prdvidei'aj process for the coloration of organic de tives c iif cellulose, wool and silk. A further obJect'is to provide colored textile materials which arefof goodx-iastness to light. and washing. A particular object of our; invention is to provide a new class of nuclear non-sulfonated azo dyes suitable forjthe coloration of cellulose acetate silk. Other objects willhereinafter appear.

'lypical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate or cellulose butyrate and the hydrolyzedas well as the unhydrolyzed mixed organic acid esters of cellulose is a methylene trative and not limitative ofthose that ester,

such as cellulose acetate-propionate, cellulose acetate-butyrate and the cellulose ethers such as methyl cellulose, ethyl cellulose or benzyl cellulose. While our invention will be illustrated more particularly in connection with the coloration of eellulose acetate silk, a. material to which the invention is especially adapted, it will be understood that it applies to the coloration of other organic derivatives of cellulose such as those Just named as Well as to the coloration of wool and silk.

The azo dye compounds of our inventidn'ban be prepared by diazotizing 'diazotizable members selected from the group consisting of an arylamine aminobenzothiazole and an aminobenzoxazole and coupling the diazonium compounds obtained;

with the coupling compounds having th formula:

wherein R1, R2, X and Y have the meanin we N .1

for example. illustrative of "cycloalkyl groups may be mentioned cyclobutyl, cyclohexyl, and cycloheptyl. Similarly, illustrative of furyl may tetrahydrofurfuryl, 5-ethylfuryl droxyethyltetrahydrofurfuryl. ,1

The nuclei represented by R and R1 can be substituted or unsubstituted. iThese nuclei can be and,

substituted, for example, with the substituent groups customarily appearing on such muclei. .As is understood in the art these nucleiican be substituted with substituents such as a'flnitroigroup, a halogen atom, an alkyl group, an alkoxy group,

e general are dissolved in a dilute aqueous hydrochloric acid solution and the resulting solution is cooled to a temperature approximately 0-10 C. The diazonium solutionprepared as described above is then added, With stirring, While maintaining the reaction mixture in a cooled condition.

After the addition or the diazonium solution the reaction mixture is permitted to stand for a short time following which it is slowly made neutral to Congo-red paper by the addition of sodiumacetate. Upon completion of the coupling reaction which takes place, the dye compound formed is recovered by filtration, washed with of the benzene series, an aminonaphthalene, an" 1'57Water and d ed. The dye compound obtained colors cellulose acetate silk yellow.

Example 2 jliijgrams of .p-ainmoacetophenone are diazotized and the diazonium compound obtained is coupled with 22 gra ns of Coupling and recovery of the dye compound formed can be carried out in accordance with the procedure-described in Example 1. The dye compound obtained colors cellulose acetate silk orange.

Example 3 13.8 grams of p-nitroaniline are diazotized and the diazonium compound obtained is coupledwith l0 be mentioned. a furyl radical such, as :lurfuryl,

a hydroxy group, a cyano group, 'a sulfonic "acid group, a carboxylic acid group and an acyl group. The substituents named are intended to be'illusfinay be substituted on the'nuclei in question.' The following examples illustrate the preparation of the azo dye compounds'ot our-inventi Example! r 12.8 grams of o -ch1oroaniline are dissolved in 150 cc. of water to which has been'added "25 cc.

of 36% hydrochloric acid. The resulting" solution is cooled to a temperature"approximating '0-5"C. by the addition of'ice, for example, and

the amine is diazotized by the addition'with stirring of 6.9 grams of sodium nitrite dissolved in water. Throughout the diazotization reaction which takes place the reaction mixture is maintained in a cooled condition. v

17.9 grams of m-methylphenyl g ycine methyl 31.1 grams of A emcmos 0c oc,H.ooH. CH1 p I ll ,{CIHI I I Example 4 V 2 .1.? grams oi 1ammo z-bmmelamtrobsnzene tained is coupled with 23.1grams of are di'azotized' and the diazon'iumcompouridlob- .lcoupling and recovery ofthe dye' compound formed can be carried out in accordance with the procedure described in Example 1. The dye comzene are diazotized and'the diazonium compound ears zoo 23 are diazotized and the diazonium compound obobtalned is' coupled with an'equivalent gram The dye compound obtainedcolorszcellulose acew ri v tate silk red.

18 grams of 6-methoxy-2-aminobenZothiaZoleE--' blue l 15 2414 grams r dianisidine are diazotized and the ediazonium omp un btained is, coup d w th 26. 8 grams of 1 are diazotizecl in nium compound obtained is coupled with 27.1

grams of CHaC-O-CHaCHOHCHaOH mo-o-omcmon tatesilk red.

Example 11 s le f amino: dinhmbmzem Coupling can carried out in an acetic 92d efonethylamide' is diazotized and the diazonium solution followed byjneutralization of the reaction 'om 'jdflfid obtained is coumed with 1 gram mole mixturewith sodiumcarbonate. When couplin of is complete water is added to the reaction mixture .v 00,11,

and the dye compound formed is recovered b l CHCEOH fl1tration',washed withwater-ar'id'dried'.""The'dye;

compound obtained colors cellulose acetate silk 1." orange. e I N-c-om n Example 7 O grams i -m thox -zam no e zoxazple I I I 4 are diazotized in known fashion and the'diazonifijgffififlfg Obtamed colors cellulose ace um compound obtained is coupled with 30.3 Example 12 grams of /OH2CHOHCH,OCH3 1 grammole of p-mtroaniline is diazotized and N lam--' ---.the diazomum oompoundobtamedls coupledtwlth cine-own, 2. lsrammolevof' H I .7 w "cm t -ooini The dye compound obtained colors cellulose acev tate silk 9. wine shade. Y 1 The dye'compound obtained colors cellulose acetate silk orange. v

Example 8 By the substitution of -1 grammole or 18.3 gramsof 1-amino-2,4-dinitrobenzene arena diazotized and the diazonium compound obtained is coupled with 28.7 grams of omcmomon N o a for the coupling component of the example a. dye I ..9. i .fiT99L... 2- 'compound'is obtained whichsimilarly colors cellulose acetate silk orange. a l r The following tabulation further illustrates the Coupling can be carried out in a. cold dilute hy- Q5 compounds included within the scope of our indrochloric acidz-solution inthemsualkmanriertvention' together with the colors they produce on The dye compoundpbtained colors cellulose acecellulose acetate silk; The compounds-indicated tate silk rubine. p below may be prepared by diazotizing the amines v, Emmp le Y l p g listed under the headingffAmine? and, coupling 33.2 grams of 70 the diazonium compounds obtained with the com- 00m pounds specified in the column entitled Coul l pling component. The diazotizationfand cou- 0 1513: v I pling reactionsrmay; for ,ex'amplebej carried out" Example 6 The dye compound obtained colors cellulose ace- O Y i The dye compound obtained colors cellulose acefollowing 1 the general procedure 'describedhere- 4 o l-amiuo-Z-acetomitrobenzene :tives'of'cellulo'se'as well as web v Nuclear sulfonated compounds; of our inven'-i*35 mine pl il ns coml fi nt v p Color m-Amiuobeuzomide mam Yellow. 2,4-dichloroeniline. .do Yellow to orange-y llow. 2,4-diiodoaniline... "f Do.

Red

1-amino-2-methoxyA-nitrobenzeue V7 to 13 above.

2,4 dinitroanil1ne 1 to 13 above 1 amino 2,4 dinitro 6 (Cl, Br)

Rub iue to purple. Rubine to violet.

mino-d-methoxy-bentoxaz Wine to violet Orange-yellow; Red to rubine. Rubine to purple. Wine. Blue.

' Rubiue to purple.

Purple.

Bmer

Violet. Greenish-blue.

Orange-red. Do.

benzene. l-amlno-z-methyH-nitrobenzene..,

sn'aaaarnntet'y'i' I sulio I; M

Blue. Greenish-blue.

the application of the nuclear non-sul- 1 fonated dye compounds of our invention has been described more particularly in connection with the coloration of cellulose acetate silk, it will be understood that these dye, C mpounds:- yield 'eI'i-,

er'ally' similar' shades on i other. 'rg'a'n'i @i sflk tion can be'prepared by sulfonation of the runner" non-sulfonate'd compounds in accordance with known sulfonation method's orby the use of previously sulfonated components. Suitable sulfoin the preparation of compounds of our invention include; forlexample;pesulfanilic ,acid- 1 amino-4,- sulfonic naphthalene; 2-naphthyl-amine S-sulfonic acid,- I-naphthylamine-3 sultonic acid,

1-naphthylamine 5esulfonicacid, .1 naphthyl- 4 amine-G-sulfonic acid, l-naphthylamine fisulfonic acid, 1-naphthylamine-3,8-disullonic acid, l-amino-5-naphthol-7-sulionic acid, metanilic acid, 1-amino-2-sulfonic-4-nitrobenzene,

l-amino-2,4-disulfonicbenzene and 1-amino-2- 5 ch1oro-4-sulfonic benzene.

Although a large number of examples of dye compounds have been given, it'isr to-be understoodv i that these examples are illustrative and not limi=.-'

tative of our invention. Any-of thediazocomr-x-ES ponents shownherein, for example;:"can beHcou-z pled with any soi the coupling components shown to 1 give compounds included within the scope; of our invention.

In order that the preparation of the compounds of our invention may be entirely clear, it is here understood' that' the types not-described 'can" be" While all 70 preparedby methodslanaloous tothose employed 1 in ,the preparation; of; thetypes described.

Theazo dye. compounds of our inventionare; for the mostpart, relatively insoluble in water. Those compounds whichare insoluble in water may be advantageously employed for the direct .dyeing ,pf; textile; materials; by grinding the dye] to afine powder, intimatelymixing itwith a suitabledispersing or .s olubilizing agent andiadding the resulting mizitureto water or a dilute solution of soap in water to-form an aqueous dyebath. Following'this known preparation of the nated amines that can be diazotized and employed 0 dyebathgth e textile materials to be dyed may be.

'tl'ie"'dybath fand" the dyeing operation I own fashionl The dyecompounds 1' of ourfinv'ention which are water soluble do notJjf of course','require'the"use of a'dispersin'gor s'olu-* 5bilizing agent but maybe applied tosilk, wool added nd c ed n and (depending upon the nature and position of the water-solubilizing groupy-organic derivative of cellulose textile rnate'rials from an aqueous solution of the dye which may contain salt. For a more complete description as to how the azo dye compounds o f ourinvjention may be employed in dyeing coloring operations, reference may be had to I S Letters BatentNo.'2;1l5,030, issued April 26 wherein R. representsthe residue of a member selected from'the group consisting of a benzene, av naphthalene, benzoxazoletand a benzothiazole nucleus'Ri represents the residue of a member selected from"the groupconsisting of a benzene .and' a "naphthalene nucleus containing but one benzene and rnaphthale'ne ringg respectively, 'Ra? 385L: a mordetaliled des'cription to how'the watersoluble az o"d'y'e's or our 7; invention may be employed for the colorationof' textile materials made of or containing organic represents a member selected from the group con carbon alkyl, 0. furyl and a phenyl nucleus and sisting of hydrogen, an aliphatic group, a cyclowherein the alkyl group, a furyl group, a phenyl nucleus anda r I -x+.c-Y Iv [I 1/,

X-'-COY group, X represents a. short chain saturated s11- phatic hydrocarbon group, Y represents a memv ber selected from the group consisting 012a hy- 8 7 9 a a to the nucleus r se t d b R1 drocarbon alkyl, a jury] and a phenyl nucleus and 10 in D r p itlon to the am bond shown. wherein t I 1 .7 I 4,14 celluloseacetate coloredwith a nuclear non-suli'onated azo dye compound havingthe group is attached to the nucleus represented R1 in para position to the azo bond shown.

2. An organicderivative, of cellul color wlilertem R'repieaenmmhef i o member with a nuclear non-sulfonated azo dye compound 20. ed from we group-cons of a benzene having the general formula:

R H V nucleus, R1 represents the residue of a member a'naphthalene, a benzoxazole and a benzothia'zole 1 selected Iromthe group consisting Ofabenzene R-N=N.-ru- N 7 v 7 and'a naphthalene nucleus containing butane,-

1 x fi oy benzene and naphthalene ring, respectively B/l 0 I consisting or hydrogen, an aliphatic groupie or wherein R represents the residue of a member cloalkyl group, a fury] group, a phenyl nucleus selected from the group consistingoiabenzene; anda" I I a naphthalene; a benzoxazole and abenz'othiazole a nucleus, R1 represents'theresidue of a member I 1 selected from the group -consisting-oia; benzene and a naphthalene nucleus containing but one benzene and naphthalene ring; respectively, R2; represents a. member selected from the group consisting of-hydrogen, an aliphatic group, a'cyclo-y group, X represents a short chain saturated aliphatic hydrocarbongroup, Y represents amemalkyl group, a furyl group, a phenyl nucleus and a I ..x.. fi oy. 1-, T M I I H v n N v H group, x represents a short maintained-n1 phatic hydrocarbon group, Y represents a. memrepresents a member, selected from the, groupber selected iron; the group consisting of a hydro-; ,a carbon alkyl, a furyl and a phenyl nucleus and ber selected from the 'grouplconsistinglof a hy'- 8rd? m to thenucl'ells represented 9 dr'ocarbon alkyl. a furyl and a Phenyl nucleus and R1 in th'azo bondkhow'ril wherein x 5,4 celluloseacetate "colored witl'i'a nuclear h s R nonj-sulfonatedazo'dye'cdmpound having the generaliormula: R M

r i 1 I 0- -'fi=- n-N -N-sr-N group is attached .to the nucleus representediby 0" R1 in para position to the azo bond'shown. 3. An organic derivative of cellulose .colored. with a nuclear non-sulionated azo dye, compound havingthe general formula:- I. r

wherein R represents the residue of :a. benzene resents'a member selected from the group-con-- nucle'us', R1 represents the residue of a benzene nucleus-containing but one benzene ring, R2 rep-,.

V p sisting 'ofhydrogen, an aliphatic group, a cy- R--N=NRr-N clo-alkyl T810119, a furyl group, a phenyl nucleus o mda A X-(fis-OY 50 v I wherein R represents the residue oi ab enz ene .ljfr j nucleus, R1 represents the residue of a benzene m x sh-ort chain nucleus containing but one benzene ring, R: rep- 5 pheiighydmarbim group Y repersents m resents a member selected from the group conher algcted'fmmthe group consisting of hydro sisting of hydrogen-,--an aliphatic group, a cycalv'bbnivalkyhafmql e w s effi l cloalkyl group, a furyl group, a phenyl nucleus Wig es d w H q r U. -'x-o- -or. .e..w R1-N l is '1 -(!'T- -0" group, X represents a short chain saturated oli- P h I 1 a phatic hydrocarbon group, Y represents a memgroup is attached to the nucleus represented by:

her selected from the group consisting of a hydro- -R11l1 paraposition to the azo pond shown.

6. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the general formula:

X-fi-O-hydrocarbon alkyl wherein R represents the residue of a benzene nucleus, R1 represents the residue of a benzene nucleus containing but one benzene ring, I; represents a short chain saturated aliphatic hydrocarbon group and wherein the hydrocarbon alkyl X-(fi-O-hydrocarbon alkyl 0 group is attached to the nucleus represented by R1 in para position to the am bond shown.

8. The azo dye compounds having the general formula:

wherein Z, and Z1 each represents a member selected from the group consisting of hydrogen,

hydroxy, a nitro group, a halogen atom, an alkyl group, a sulfone group, a sulfonamide group, a ketone group and a cyano group, R1 represents the residue of a benzene nucleus containing but phatic group,-a cyoloalkyl group, a furyl group, a

one benzene ring, R2 represents a member selected from the group consisting of hydrogen, an ali phenyl nucleus and a x-( -oY group, X represents a shortchain] saturated aliphatic hydrocarbon group, Y represents a member selected frorn'the group consisting of a hydrocarbon-alkyl, a furyl and a phenyl nucleus and wherein the --Ri--N group is attached to the nucleus represented by R1 in para position to the azo bond shown.

9. The 'azo dye compounds having the general formula:

v H R-N==N-'R1N/ X-(l.'|l-0-hydroearbon alkyl 7 I 0 wherein R represents the residue of a benzene nucleus, R1 represents a' residue of a benzene nucleus containing but one benzene ring, X represents a short chainsaturated aliphatic hydrocarbon group and wherein the --Ri-N X-("l-0- -hydr ocarbon alkyl 0 group is attached to the nucleus represented by R1 in para position to the azo bond. I

10. 'Theazo dye compounds having the general formula:

' hydrocarbon alkyl RN=N-R1 X-(]?-O-hydrocarbon alkyl o I wherein R represents the residue of a benzene nucleus, R1 represents the residue of a benzene nucleus containing but one benzene ring, X represents a short chain saturated aliphatic hydrocarbon group and wherein the hydrocarbon alkyl "Rx-N X-(fi -O-hydrocarbon alkyl 0. group is attached to the nucleus represented by R1 in para position to the am bond.

' JAMES G. McNALLY.

JOSEPH B. DICKEY. 

